EP0090787B1 - A process for making bis (hydroxyphenyl)-methanes - Google Patents
A process for making bis (hydroxyphenyl)-methanes Download PDFInfo
- Publication number
- EP0090787B1 EP0090787B1 EP83870029A EP83870029A EP0090787B1 EP 0090787 B1 EP0090787 B1 EP 0090787B1 EP 83870029 A EP83870029 A EP 83870029A EP 83870029 A EP83870029 A EP 83870029A EP 0090787 B1 EP0090787 B1 EP 0090787B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phenol
- hydroxyphenyl
- bis
- formaldehyde
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
Definitions
- This invention relates to a process for the preparation of bis(hydroxyphenyl)methanes by the reaction of phenol and formaldehyde in the presence of aqueous phosphoric acid.
- Sulfuric acid processes are undesirable for several reasons including: the tendency to form sulfonated products, generating severe discoloration of the reaction products and making separation of the aqeuous and organic phases difficult; the need for dilute acid solutions to minimize sulfonation; and the requirement of high ratios of acid to phenol to obtain high concentration of diphenol in the reaction product.
- British Patent No. 711.122 describes a process for the production of bis-(hydroxyphenyl) compounds, which comprises reacting phenolic compounds with carbonyl compounds in an aqeuous acidic medium containing an amount of water equal to at least twice the weight of said phenolic compounds.
- An Example describes the use of an acidic medium comprising 2 g of phosphoric acid in 300 g of water and 2 g of alkyl aryl sulphonate, in the reaction of 100 g of 2-tertiary-butyl-4-methylphenol with 29 g. of 36% aqueous formaldehyde at 100°Cto make bis-(3-tert.butyl-5-methyl-2-hydroxyphenyl)methane.
- the process of the invention is one for producing a bis(hydroxy-phenyl)methane which comprises reacting phenol and formaldehyde in the presence of water and phosphoric acid, characterised by effecting the reaction at a temperature from 20 to 60°C in a two phase mixture containing at least 3 moles of phenol per mole of formaldehyde and an aqueous solution of phosphoric acid containing from 0.5 to 8 moles of phenol per mole of phosphoric acid and from 1.5 to 6.0 moles of water per mole of phosphoric acid to produce a bis(hydroxyphenyl)methane and separating the organic phase containing the bis(hydroxyphenyl)methane from the aqueous phase.
- the mole ratio of phenol to formaldehyde is in the range of 3 to 20
- the mole ratio of phenol to phosphoric acid is in the range of 0.5 to 8
- the mole ratio of water to phosphoric acid is in the range of 1.5 to 6.
- the preferred mole ratios are in the following respective ranges 4 to 6; to 4 and 2.5 to 3.0.
- a high ratio of phenol to formaldehyde minimizes byproduct formation but greater energy consumption is caused by the greater load of recycled unreacted phenol.
- a higher acid ratio gives a faster reaction rate but increases the energy consumption because of the greater load of recycled acid.
- phenol to acid mole ratios in the range of about 2 to about 4 give a high yield in the range of about 90 percent of bis(hydroxyphenyl)methanes.
- the first step is the addition of formaldehyde to phenol to form a mixture of about 60 percent 4-(hydroxymethyl)phenol and 40 percent 2-(hydroxymethyl)phenol.
- the 4,4'-bis(hydroxyphenyl)methane content of the bis(hydroxyphenyl)methane product can be varied in the range of 55 to 75 percent, the oligomeric by-product increasing with the concentration of 4,4'- isomer.
- Reaction conditions can be selected so that the yield of bis(hydroxyphenyl)methanes based on formaldehyde is at least about 80 percent. Indeed yields of 90 percent have been obtained, with the recovered product containing 92 to 94 weight percent of bis(hydroxyphenyl)methanes of which 55 percent is 4,4'-bis(hydroxyphenyl)methane.
- the yield based on formaldehyde is about 68 percent and 74 weight percent of the total product is bis(hydroxyphenyl)methane and 26 weight percent is oligomeric.
- the mole ratio of water to phenol for good selectivity of the 4,4'-isomer and good yield of bis(hydroxyphenyl)methanes is preferably about 1.0.
- the phenol and aqueous acid are mixed intimately and the formaldehyde is added continuously throughout the reaction so that the instantaneous phenol formaldehyde ratio is much greater than it would be if all the formaldehyde were added initially and the concentration of 2-(hydroxymethyl) phenol is severely limited, preventing the formation of appreciable amounts of oligomer. Since the ratio of phenol to formaldehyde is always high the rate of addition of formaldehyde can be linear throughout the reaction or can be reduced throughout the reaction.
- the reaction can be carried out at any temperature in the range of about 20 to about 60°C. If the temperature is below about 40°C a solvent can be advantageously added to the organic phase to maintain phenol and the bis(hydroxyphenyl)methanes in solution. Suitable solvents include toluene, xylene and dichloromethane. At temperatures above about 60°C, the rate of reaction of 2-(hydroxymethyl)phenol and 4-(hydroxymethyl)phenol with bis(hydroxyphenyl)methanes is increased thus decreasing the yield of bis(hydroxyphenyl)methanes. It is therefore preferable to carry out the reaction at a temperature in the range of about 40 to about 50°C and more preferably in the range of about 43 to about 47°C.
- the 4,4'-isomer may begin to precipitate.
- Precipitation can, of course, be enhanced at the completion of the reaction by lowering the batch temperature. Separation of the solids by filtration or centrifugation is very difficult and tedious because of the fine particle size of the solids. A stable high viscosity emulsion is formed. Easy separation is achieved by raising the batch temperature, after completion of the reaction, to 65-70°C to dissolve any solids in the phenol phase. Reduced agitation permits greater coalescence of the dispersed phase. When agitation is then stopped, separation of the two liquid phases is rapid and very complete.
- phosphoric acid 85 percent phosphoric acid but the acid can be obtained from any source such as by dissolving phosphorus pentoxide in water.
- Formaldehyde is conveniently supplied by formalin solutions, in the range of 37-50 weight percent. However other concentrations and other sources such as trioxane, paraformaldehyde and methylal can be used.
- Residual acid in the organic phase is partly neutralized by the addition of 4 parts of solid sodium bicarbonate with agitation to provide a pH of about 5.0. Alkaline pH must be avoided to prevent color development. Carbon dioxide evolved in the neutralization is vented to the atmosphere. The sodium dihydrogen phosphate which precipitates is removed by filtering. The viscosity of the organic phase after filtration is about 10 cp. The organic phase is concentrated by removing water and unreacted phenol under vacuum. The temperature is raised to 120°C and distillation is initiated at about 425 torr. The pot temperature is gradually raised to 140°C and distillation is continued until the pressure has been reduced to 1 torr. 159 parts of phenol and 13 parts of water are distilled.
- the residue is about 90% bis(hydroxyphenyl)methane and 10% oligomers. Residue solidification occurs at roughly 120°C. Contact with air is minimized when material is hot to prevent color formation. Distillation of the phenol-stripped material is continued at 1 torr to a pot temperature of 230°C.
- the distillate comprises 100 parts of bis(hydroxyphenyl)-methanes. 4,4'-bis(hydroxyphenyl)methane is the highest melting and boiling isomer.
- the freezing point of 4,4'-bis(hydroxyphenyl)methane is about 162°C, that of the 2,4'-isomer is 120°C, and that of the 2,2'-isomer is 119°C.
- the distillate is kept at 160°C or above to prevent freezing. It can be poured into shallow pans for cooling and crystallizing. Again, contact with air must be prevented as much as possible when the material is hot.
- Determination of isomers in the synthesis products is carried out by liquid chromatography in a Waters 6000A liquid chromatograph with U.V. detector (254 nm) and C 28 p Bondapak column.
- the eluant solution consists of 39% freshly distilled tetrahydrofuran, 60% distilled water and 1% acetic acid, degassed and at ambient temperature.
- the eluant flow rate is 1 ml/min.
- the analytical sample consists of 1 g. of reaction product diluted to 100 ml. with the tetrahydrofuran/water solution.
- peaks are generally seen in a typical chromatogram. Proper identification of the components of interest is important. The retention time of a peak may be affected by several factors that may differ significantly from chromatograph to chromatograph and from one batch of solvent to the next. Thus, more useful parameters for peak identification must be used. Two of the most useful parameters for peak identification are the retention factor (k) and the relative retention (a).
Description
- This invention relates to a process for the preparation of bis(hydroxyphenyl)methanes by the reaction of phenol and formaldehyde in the presence of aqueous phosphoric acid.
- Heretofore, the preparation of bis(hydroxyphenyl)methanes has been carried out by reaction of phenol and formaldehyde in the presence of strong mineral acids such as hydrochloric and sulfuric acids. Hydrochloric acid catalyzed processes suffer from several disadvantages: the volatility of hydrogen chloride gas; the corrosiveness of hydrochloric acid; the tendency to produce chloromethyl ether and chloromethylphenols; and the use of relatively dilute acid which makes separation of the aqueous and organic phases and recycle of the acid phase difficult. Sulfuric acid processes are undesirable for several reasons including: the tendency to form sulfonated products, generating severe discoloration of the reaction products and making separation of the aqeuous and organic phases difficult; the need for dilute acid solutions to minimize sulfonation; and the requirement of high ratios of acid to phenol to obtain high concentration of diphenol in the reaction product.
- British Patent No. 711.122 describes a process for the production of bis-(hydroxyphenyl) compounds, which comprises reacting phenolic compounds with carbonyl compounds in an aqeuous acidic medium containing an amount of water equal to at least twice the weight of said phenolic compounds. An Example describes the use of an acidic medium comprising 2 g of phosphoric acid in 300 g of water and 2 g of alkyl aryl sulphonate, in the reaction of 100 g of 2-tertiary-butyl-4-methylphenol with 29 g. of 36% aqueous formaldehyde at 100°Cto make bis-(3-tert.butyl-5-methyl-2-hydroxyphenyl)methane.
- There has now been found an improved phosphoric-acid-catalysed process for the preparation of bis(hydroxyphenyl)methanes of improved color, and in high yield, in which the ratio of phenol to acid catalysts is substantially higher than in other catalysed processes. Surprisingly the low solubility of phenol in phosphoric acid and conversely of phosphoric acid in phenol does not impair the reaction rate but greatly aids product separation and catalyst recycle.
- The process of the invention is one for producing a bis(hydroxy-phenyl)methane which comprises reacting phenol and formaldehyde in the presence of water and phosphoric acid, characterised by effecting the reaction at a temperature from 20 to 60°C in a two phase mixture containing at least 3 moles of phenol per mole of formaldehyde and an aqueous solution of phosphoric acid containing from 0.5 to 8 moles of phenol per mole of phosphoric acid and from 1.5 to 6.0 moles of water per mole of phosphoric acid to produce a bis(hydroxyphenyl)methane and separating the organic phase containing the bis(hydroxyphenyl)methane from the aqueous phase.
- Advantageously the mole ratio of phenol to formaldehyde is in the range of 3 to 20, the mole ratio of phenol to phosphoric acid is in the range of 0.5 to 8 and the mole ratio of water to phosphoric acid is in the range of 1.5 to 6. The preferred mole ratios are in the following respective ranges 4 to 6; to 4 and 2.5 to 3.0.
- A high ratio of phenol to formaldehyde minimizes byproduct formation but greater energy consumption is caused by the greater load of recycled unreacted phenol. Similarly a higher acid ratio gives a faster reaction rate but increases the energy consumption because of the greater load of recycled acid. Indeed it is an advantage of the present process that phenol to acid mole ratios in the range of about 2 to about 4 give a high yield in the range of about 90 percent of bis(hydroxyphenyl)methanes. Water plays a significant role in the reaction, affecting both the yield of bis(hydroxyphenyl)methanes and the selectivity. The amount of water depends to some extent on the reaction temperature and the acid catalyst ratio.
- In the reaction of phenol and formaldehyde, the first step is the addition of formaldehyde to phenol to form a mixture of about 60 percent 4-(hydroxymethyl)phenol and 40 percent 2-(hydroxymethyl)phenol.
- The most noticeable effect of water is the inhibition of the reaction of 2-(hydroxymethyl)phenol and phenol with the result that the formation of a predominant amount of 4,4'-bis(hydroxyphenyl)methane, a minor amount of the 2,4'isomer and a negligible amount of the 2,2'-isomer occurs. It is believed that because the reaction of 2-(hydroxymethyl)phenol with phenol and with bis(hydroxyphenyl)methanes is inhibited, it tends to react with more formaldehyde forming 2,4- and 2,6- dihydroxymethylphenols which then form oligomers. With adjustment of the reaction conditions the 4,4'-bis(hydroxyphenyl)methane content of the bis(hydroxyphenyl)methane product can be varied in the range of 55 to 75 percent, the oligomeric by-product increasing with the concentration of 4,4'- isomer. Reaction conditions can be selected so that the yield of bis(hydroxyphenyl)methanes based on formaldehyde is at least about 80 percent. Indeed yields of 90 percent have been obtained, with the recovered product containing 92 to 94 weight percent of bis(hydroxyphenyl)methanes of which 55 percent is 4,4'-bis(hydroxyphenyl)methane. When conditions are changed to provide bis(hydroxyphenyl)methanes containing about 75 percent of the 4,4'-isomer, the yield based on formaldehyde is about 68 percent and 74 weight percent of the total product is bis(hydroxyphenyl)methane and 26 weight percent is oligomeric. The mole ratio of water to phenol for good selectivity of the 4,4'-isomer and good yield of bis(hydroxyphenyl)methanes is preferably about 1.0.
- Advantageously, when the reaction is carried out, the phenol and aqueous acid are mixed intimately and the formaldehyde is added continuously throughout the reaction so that the instantaneous phenol formaldehyde ratio is much greater than it would be if all the formaldehyde were added initially and the concentration of 2-(hydroxymethyl) phenol is severely limited, preventing the formation of appreciable amounts of oligomer. Since the ratio of phenol to formaldehyde is always high the rate of addition of formaldehyde can be linear throughout the reaction or can be reduced throughout the reaction.
- The reaction can be carried out at any temperature in the range of about 20 to about 60°C. If the temperature is below about 40°C a solvent can be advantageously added to the organic phase to maintain phenol and the bis(hydroxyphenyl)methanes in solution. Suitable solvents include toluene, xylene and dichloromethane. At temperatures above about 60°C, the rate of reaction of 2-(hydroxymethyl)phenol and 4-(hydroxymethyl)phenol with bis(hydroxyphenyl)methanes is increased thus decreasing the yield of bis(hydroxyphenyl)methanes. It is therefore preferable to carry out the reaction at a temperature in the range of about 40 to about 50°C and more preferably in the range of about 43 to about 47°C.
- When the concentration of bis(hydroxyphenyl)methanes rises above approximately 40 weight percent, the 4,4'-isomer may begin to precipitate. Precipitation can, of course, be enhanced at the completion of the reaction by lowering the batch temperature. Separation of the solids by filtration or centrifugation is very difficult and tedious because of the fine particle size of the solids. A stable high viscosity emulsion is formed. Easy separation is achieved by raising the batch temperature, after completion of the reaction, to 65-70°C to dissolve any solids in the phenol phase. Reduced agitation permits greater coalescence of the dispersed phase. When agitation is then stopped, separation of the two liquid phases is rapid and very complete.
- After decantation, it is essential that any residual acid in the phenol phase be neutralized before proceeding to temperature conditions of 100°C and higher. Otherwise, the bis(hydroxyphenyl)methanes are rapidly degraded to higher molecular weight material (Novolac resins) and phenol. After neutralization, the preferred pH range is 4.5-5.5 (substitution for one acid hydrogen atom). Alkaline pH must be avoided to prevent color development.
- To lessen the loss of bis(hydroxyphenyl)methanes and phenol caused by absorption on the filtered or settled salt after neutralization of the phenol phase, it may be necessary to wash the salt with methanol or hot phenol and recover the bis(hydroxyphenyl)methanes from the washings.
- The most readily available and lowest cost source of phosphoric acid is 85 percent phosphoric acid but the acid can be obtained from any source such as by dissolving phosphorus pentoxide in water. Formaldehyde is conveniently supplied by formalin solutions, in the range of 37-50 weight percent. However other concentrations and other sources such as trioxane, paraformaldehyde and methylal can be used.
- The following examples set forth methods of carrying out the process of the invention but should not be regarded as limitations thereof. Unless otherwise indicated parts and percentages are by weight.
- 130 parts of 85% phosphoric acid is added to 265 parts of freshly distilled liquid phenol (F.P. 40.8°C) in a nitrogen-blanketed, stirred stainless steel reactor and the temperature is adjusted to 45°C. A two-phase mixture is formed and is stirred vigorously to thoroughly disperse the aqueous acid phase. 45.75 parts of 37% formalin is then metered at about 1.1.4 parts per hour to the reaction mixture over a 4 hr. period. The reaction temperature is controlled at 45 ± 2°C during the formalin addition and for 30 minutes thereafter. When conversion proceeds to the point where the bis(hydroxyphenyl)methane concentration is about 40% by wt. of the phenol phase, some 4,4' isomer precipitates and the mixture viscosity rapidly changes from about 100 to 1000 cp, and a crystallization exotherm is observed. Formaldehyde conversion to bis(hydroxyphenyl)methanes is about 90% and the resultant isomer ratio is about 55/37/8 4,4'-, 2,4'-, 2,2'-isomers. The remainder of the formaldehyde is converted to higher molecular weight products. At the completion of the reaction, the temperature is raised to 65°C to dissolve any precipitated solids and the agitator tip speed is reduced by 50%. Batch temp. is maintained at 65°C for 30 minutes and then the agitation is stopped and the acid and oil phases are allowed to separate. The acid phase is drawn from the bottom of the reactor. 98-99% of the acid is recovered as a 70% aqueous phosphoric acid solution with a specific gravity of 1.5.
- Residual acid in the organic phase is partly neutralized by the addition of 4 parts of solid sodium bicarbonate with agitation to provide a pH of about 5.0. Alkaline pH must be avoided to prevent color development. Carbon dioxide evolved in the neutralization is vented to the atmosphere. The sodium dihydrogen phosphate which precipitates is removed by filtering. The viscosity of the organic phase after filtration is about 10 cp. The organic phase is concentrated by removing water and unreacted phenol under vacuum. The temperature is raised to 120°C and distillation is initiated at about 425 torr. The pot temperature is gradually raised to 140°C and distillation is continued until the pressure has been reduced to 1 torr. 159 parts of phenol and 13 parts of water are distilled. The residue is about 90% bis(hydroxyphenyl)methane and 10% oligomers. Residue solidification occurs at roughly 120°C. Contact with air is minimized when material is hot to prevent color formation. Distillation of the phenol-stripped material is continued at 1 torr to a pot temperature of 230°C. The distillate comprises 100 parts of bis(hydroxyphenyl)-methanes. 4,4'-bis(hydroxyphenyl)methane is the highest melting and boiling isomer. The freezing point of 4,4'-bis(hydroxyphenyl)methane is about 162°C, that of the 2,4'-isomer is 120°C, and that of the 2,2'-isomer is 119°C. The distillate is kept at 160°C or above to prevent freezing. It can be poured into shallow pans for cooling and crystallizing. Again, contact with air must be prevented as much as possible when the material is hot.
- Determination of isomers in the synthesis products is carried out by liquid chromatography in a Waters 6000A liquid chromatograph with U.V. detector (254 nm) and C28 p Bondapak column. The eluant solution consists of 39% freshly distilled tetrahydrofuran, 60% distilled water and 1% acetic acid, degassed and at ambient temperature. The eluant flow rate is 1 ml/min. The analytical sample consists of 1 g. of reaction product diluted to 100 ml. with the tetrahydrofuran/water solution.
- Several peaks are generally seen in a typical chromatogram. Proper identification of the components of interest is important. The retention time of a peak may be affected by several factors that may differ significantly from chromatograph to chromatograph and from one batch of solvent to the next. Thus, more useful parameters for peak identification must be used. Two of the most useful parameters for peak identification are the retention factor (k) and the relative retention (a).
-
- 25.7 parts (.273 mole) of phenol is dissolved in 20 parts of toluene and the solution cooled in a constant temperature bath controlled at 10°C. In a separate vessel 5.8 parts of 37% formalin (.072 moles CH20) is added to 16.2 parts of 85% phosphoric acid (0.142 mole H3P04) with stirring and the mixture is cooled to 10°C. The phosphoric acid/formalin solution is added to the stirred phenol/toluene solution. The two phase reaction mixture is stirred for about 20 hrs. at 10°C. The reaction mixture is diluted with 40 parts of methyl alcohol giving a hom_ogeneous solution. The reaction mixture is analyzed by liquid chromatography. The yield of bis(hydroxyphenyl)methane based on formaldehyde is about 69% and the isomer ratio is 76.2/22.3/ 1.4, 4,4'-, 2,4'-, 2,2'-isomers respectively.
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/362,719 US4400554A (en) | 1982-03-29 | 1982-03-29 | Process for making bis(hydroxyphenyl)methanes |
US362719 | 1989-06-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0090787A1 EP0090787A1 (en) | 1983-10-05 |
EP0090787B1 true EP0090787B1 (en) | 1985-09-18 |
Family
ID=23427248
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83870029A Expired EP0090787B1 (en) | 1982-03-29 | 1983-03-24 | A process for making bis (hydroxyphenyl)-methanes |
Country Status (5)
Country | Link |
---|---|
US (1) | US4400554A (en) |
EP (1) | EP0090787B1 (en) |
JP (1) | JPS58177928A (en) |
CA (1) | CA1181431A (en) |
DE (1) | DE3360820D1 (en) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2580275B1 (en) * | 1985-04-16 | 1988-11-18 | Nouvel Colette | IMPROVED PREPARATION AND APPLICATIONS OF SUBSTITUTED BISPHENOLS |
JPH06128183A (en) * | 1992-02-27 | 1994-05-10 | Mitsui Toatsu Chem Inc | Method for simultaneous production of bisphenol f and novolak type phenolic resin |
DE4223979C2 (en) * | 1992-07-21 | 1995-07-06 | Rwe Ges Fuer Forschung Und Ent | Process for the preparation of 2,4-dimethylphenol |
JPH06211715A (en) * | 1993-01-22 | 1994-08-02 | Mitsui Toatsu Chem Inc | Production of bisphenol f |
JP2005187450A (en) * | 2003-12-01 | 2005-07-14 | Nippon Steel Chem Co Ltd | Method for producing bisphenol |
JP5148811B2 (en) * | 2004-06-29 | 2013-02-20 | 新日鉄住金化学株式会社 | Method for producing bisphenols |
JP2006016335A (en) * | 2004-07-01 | 2006-01-19 | Asahi Organic Chem Ind Co Ltd | Method for producing tetrakis(hydroxyphenyl)alkane |
JP4585251B2 (en) * | 2004-08-05 | 2010-11-24 | 旭有機材工業株式会社 | Method for producing bisphenols |
CN101429273B (en) * | 2008-12-17 | 2010-12-08 | 湘潭大学 | Process for producing wind electricity grade of bisphenol F epoxy resin |
CN102516035B (en) * | 2011-12-19 | 2014-04-09 | 胶州市精细化工有限公司 | Preparation method of bisphenol F |
CN102992964A (en) * | 2012-10-08 | 2013-03-27 | 山东莱芜润达新材料有限公司 | Method for producing bisphenol F |
CN103319314B (en) * | 2013-06-09 | 2015-10-28 | 陕西师范大学 | The synthetic method of Bisphenol F under salt bath system |
EP3046898B1 (en) | 2013-09-20 | 2019-11-06 | Aditya Birla Chemicals (Thailand) Ltd. | Improved manufacturing process for dihydroxydiphenylmethane with high selectivity for 2,4'- dihydroxydiphenylmethane |
CN103772154B (en) * | 2014-01-21 | 2016-03-09 | 湘潭大学 | A kind of modified hydroxylapatite catalyzes and synthesizes the method for Bisphenol F |
CN103936561A (en) * | 2014-05-07 | 2014-07-23 | 江南大学 | Method for synthesizing bisphenol F by virtue of efficient catalysis of mixed sulfonic acid and phosphoric acid |
CN103922897A (en) * | 2014-05-07 | 2014-07-16 | 江南大学 | Novel method for efficiently synthesizing bisphenol F with boric acid serving as auxiliary catalyst |
JP6244259B2 (en) * | 2014-05-07 | 2017-12-06 | 新日鉄住金化学株式会社 | Method for producing high purity bisphenol F |
CN104326879A (en) * | 2014-09-15 | 2015-02-04 | 江南大学 | New method for efficiently synthesizing bisphenol F with mixed acid as auxiliary catalyst |
CN104326878A (en) * | 2014-09-15 | 2015-02-04 | 江南大学 | Method for synthesizing bisphenol F under phosphoric acid catalysis accelerated by nitric acid |
CN104326877A (en) * | 2014-09-15 | 2015-02-04 | 江南大学 | New method for synthesizing bisphenol F under catalysis assisted by aluminum compound as additive |
CN104326876A (en) * | 2014-09-15 | 2015-02-04 | 江南大学 | New method for efficiently synthesizing bisphenol F with hydrogen peroxide and phosphoric acid as mixed catalyst |
CN104447217A (en) * | 2014-12-05 | 2015-03-25 | 四川东材绝缘技术有限公司 | Synthesis method of 4,4-bisphenol F |
CN104744304A (en) * | 2014-12-26 | 2015-07-01 | 江南大学 | Epoxy resin proplastid cyano bisphenol F and synthesis thereof |
CN105037107B (en) * | 2015-06-03 | 2017-04-26 | 湘潭大学 | Synthesis method of high-4,4'-isomer-content bisphenol F |
CN113574041B (en) * | 2019-03-18 | 2023-10-13 | 三菱化学株式会社 | Bisphenol production method and polycarbonate resin production method |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB711122A (en) * | 1951-09-22 | 1954-06-23 | Bataafsche Petroleum | Improvements in or relating to the production of bis(hydroxyphenyl) compounds |
US2812364A (en) * | 1953-09-22 | 1957-11-05 | Union Carbide Corp | Manufacture of diphenylol methanes |
GB816913A (en) * | 1955-12-30 | 1959-07-22 | American Cyanamid Co | Preparation of 2,2-methylene-bis-(4,6-dialkyl phenols) |
DE1135488B (en) * | 1959-10-03 | 1962-08-30 | Consortium Elektrochem Ind | Process for the preparation of diphenylolalkanes |
DE1135489B (en) * | 1960-07-28 | 1962-08-30 | Bayer Ag | Process for the preparation of 4,4'-dihydroxydiphenylalkanes or -cycloalkanes |
GB1467628A (en) * | 1973-04-26 | 1977-03-16 | Shell Int Research | Production of mixtures of bis-hydroxyphenyl-alkanes |
DE2418975A1 (en) * | 1974-04-19 | 1975-10-30 | Bayer Ag | Dihydroxydiphenyl-alkane prepn. from aldehydes and phenols - catalysed by acids of phosphorus with continuous removal of water formed |
-
1982
- 1982-03-29 US US06/362,719 patent/US4400554A/en not_active Expired - Fee Related
-
1983
- 1983-03-24 DE DE8383870029T patent/DE3360820D1/en not_active Expired
- 1983-03-24 EP EP83870029A patent/EP0090787B1/en not_active Expired
- 1983-03-28 CA CA000424603A patent/CA1181431A/en not_active Expired
- 1983-03-28 JP JP58050586A patent/JPS58177928A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
EP0090787A1 (en) | 1983-10-05 |
JPH0372049B2 (en) | 1991-11-15 |
US4400554A (en) | 1983-08-23 |
DE3360820D1 (en) | 1985-10-24 |
JPS58177928A (en) | 1983-10-18 |
CA1181431A (en) | 1985-01-22 |
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